JPH0356593B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyester plasticizer for synthetic resins such as vinyl chloride resins, which has excellent compatibility, bleed resistance, non-migration properties, processability, etc. Polycaprolactone homopolymer is conventionally known as a plasticizer using polycaprolactone. In addition, the patent application filed by Ciba Geigy in 1972-
No. 17928, JP-A-51-54640, JP-A-54-54641, and JP-A-56-22335 filed by Dainippon Ink and Chemicals Co., Ltd. However, polycaprolactone homopolymer has a problem of high crystallinity and powdery substances bleed onto the surface of the vinyl chloride resin. Also, Ciba Geigy and Dainippon Ink & Chemicals Co., Ltd.
The disadvantage of these was that they had a low molecular weight and migrated to the surface of the resin. The present inventors have diligently investigated these problems and have found a polyester plasticizer with excellent compatibility, bleed resistance, non-migration properties, and processability, and have completed the present invention. That is, the present invention is based on the composition formula () [A] _l [B] _n [C] _o ... () (wherein A is an aromatic dicarboxylic acid having a linear or side chain having 8 to 16 or 36 carbon atoms. Indicates residue; B
represents a diol residue having a linear or side chain having 2 to 24 carbon atoms; C represents a 6-hydroxycaproic acid residue; however, each of these residues is bonded with an ester bond to form the entire molecule. 6-hydroxycaproic acid residues are distributed randomly and/or in blocks, l, m, and n have values greater than 0,
~98% by weight) and a number average molecular weight of approximately 2000 ~
200000 is provided. In the present invention, the number average molecular weight refers to a numerical value determined by gel permeation chromatography (GPC) under the following conditions. Measurement conditions: Equipment…LC-3A (manufactured by Shimadzu Corporation) Solvent…tetrahydrofuran (flow rate 1 ml/min) Temperature…room temperature detector…ShodexRISE-11 (manufactured by Showa Denko) Column…HSG-PRE (1 piece), HSG-20 ( 1 piece),
HSG-15 (3 pieces), HSG-10 (1 piece) (all manufactured by Shimadzu Corporation) In the present invention, random and/or block-like refers to cases in which each residue is bonded in a completely random manner or It also means a random state containing partial block units, and may also be entirely in a block state, with at least C component being 20 to 98% in the copolymer.
It is sufficient if the number average molecular weight is about 2,000 to 200,000. In addition, components A and B are usually composed of approximately equal molar composition because they are bonded by an ester bond,
l, m, n have values greater than 0. In the present invention, the acid component corresponding to A in the compositional formula (), that is, a dicarboxylic acid residue having a linear or side chain having 8 to 16 or 36 carbon atoms, is an aromatic dicarboxylic acid or anhydride thereof, or an aromatic dicarboxylic acid or anhydride thereof. Dialkyl esters of group dicarboxylic acids, such as phthalic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalate, dimethyl isophthalate, dimethyl phthalate, diethyl phthalate, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride. acid,
Examples include hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylhymic anhydride. Residue A may consist of two or more types of dicarboxylic acid residues. On the other hand, the diol components corresponding to B in the composition formula () include ethylene glycol, propylene glycol, 1,4-butanediol, 2-methylpropanediol, 1,3-butylene glycol, diethylene glycol, neopentyl glycol, 1 , 6-hexane glycol, neopentyl glycol hydroxypivalate,
1,4-cyclohexanedimethanol, hydrogenated bisphenol-A, 1,2-dodecanediol,
1,4-bis(2-hydroxyethoxy)benzene, 1,4-bishydroxymethylbenzene,
Styrene glycol, 2,2-bis-4-(2-
Hydroxyethoxy) phenylpropane, bisphenol A E0 additive, propylene glycol, 2-methylpropanediol,
Diols having a side chain, such as 1,3-butylene glycol and neopentyl glycol, and diols having an oxygen atom in between, such as diethylene glycol, are effective and preferred from the viewpoint of lowering the crystallinity of the resin. Note that residue B is 2 of the diol residues.
It may consist of more than one species. On the other hand, C in the compositional formula (), that is, the 6-hydroxycaproic acid residue, is preferably derived from ε-cabrolactone, but may be derived from 6-hydroxycaproic acid itself. The content of such 6-hydroxycaproic acid residues is
It needs to be 20 to 98% by weight, preferably 60 to 90% by weight. Outside this range, it is not satisfactory as a plasticizer for vinyl chloride resins. The number average molecular weight of the polyester of the present invention is approximately 2000
~200000, preferably 5000-50000. If the molecular weight is too low, there is a drawback that it migrates to the surface of vinyl chloride, whereas if the molecular weight is too high, there is a problem in processability. The synthesis of the polyester plasticizer of the present invention is ()
ε-cabrolactone or hydroxycaproic acid,
() A hydroxyl component consisting of one or more diols having a straight chain or side chain having 2 to 24 carbon atoms; and () a dicarboxylic acid having a straight chain or side chain having 4 to 16 or 36 carbon atoms or its anhydride. A predetermined amount of an acid component consisting of one or more types of alkyl esters or lower alkyl esters is mixed, heated and stirred in the presence of an esterification promoting catalyst, and esterification reaction and polycondensation are carried out while removing generated water as appropriate. This can be obtained by doing the following. More specifically, for example, predetermined amounts of diol, dicarboxylic acid, and ε-cabrolactone are mixed, an esterification promoting catalyst is added thereto, and 150
Heating and stirring at ~230℃ under normal pressure and further under reduced pressure,
It can be synthesized by performing an esterification reaction and ring-opening addition polymerization of ε-cabrolactone while removing water produced by the esterification reaction from the reaction system. In the latter stage of the reaction, it is preferable to proceed with the condensation reaction by stirring at 200 to 230° C. under reduced pressure to remove water, further unreacted diols, and low molecular weight reactants from the reaction system. As the esterification promoting catalyst, a wide range of catalysts can be used, including organic titanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, and tetrabutoxytitanium, di-n-butyl- Examples include organotin compounds such as tin-dilaurate, di-n-butyl-tin-oxide, dibutyl-tin-diacetate, and combinations of acetates such as magnesium, calcium, and zinc with antimony oxide or the above titanium compounds. be able to. These catalysts have a
It is preferable to use it in a range of 10 to 10,000 ppm. It is not preferable for the reaction temperature to be higher than 230°C. This is because the depolymerization temperature of polycaprolactone is 220 to 230°C, so if the reaction is carried out at a higher temperature than this, the polymer will decompose and the molecular weight will not increase. In addition, as the specific dicarboxylic acid or its anhydride or lower alkyl ester and diol to be used, various acid components or its anhydrides or alkyl esters having 1 to 3 carbon atoms and diol components shown above can be applied. can. In this way, the polyester plasticizer of the present invention can be synthesized by charging all the raw materials at once. However, the method described below is more effective for synthesizing polyester with a molecular weight of 5000 or more. That is, the above-mentioned hydroxy component () and acid component () are mixed in advance and subjected to an esterification reaction and polycondensation in the presence of an esterification catalyst to obtain a linear polyester with a molecular weight of about 5,000 to 200,000,
The polyester resin of the present invention can be efficiently obtained by mixing a predetermined amount of ()ε-cabrolactone into the mixture and heating and reacting it in the presence of a high polymerization ring-opening catalyst. More specifically,
For example, a diol, a dicarboxylic acid or its anhydride or lower alkyl ester, and an esterification promoting catalyst are mixed in the above molar ratio, and the esterification reaction and polycondensation are carried out at 150 to 280°C under normal pressure or further under reduced pressure of 10 mmHg or less. After the reaction, the molecular weight is about 5000~
After synthesizing 100000 linear polyester resins, ε
- Mix cabrolactone in a predetermined ratio, add a high polymerization ring-opening catalyst of ε-cabrolactone,
The polyester resin of the present invention can be obtained by carrying out the reaction at 200°C under normal pressure. According to such a method, as well as producing a high polymer of ε-cabrolactone, the molecular weight of about 5,000 to 100,000 added to the reaction system
The linear polyester undergoes a transesterification reaction with highly polymerized polycaprolactone to produce the polyester of the present invention. In addition, there is no need to stir a highly viscous resin with a high degree of polymerization under reduced pressure for a long time, which is very advantageous industrially. The esterification promoting catalyst used in the above method is the same as described above, and the high polymerization ring opening catalyst includes chlorine,
10 to 10 stannous halides such as bromine and iodine
It is appropriate to use 5000 ppm, preferably 50 to 500 ppm. In this case, the reaction is significantly accelerated by allowing oxygen to coexist in the reaction system. The polyester plasticizer of the present invention thus obtained has a molecular weight of about 2,000 to 200,000. The polyester plasticizer of the present invention is preferably used for synthetic resins, especially halogen-containing resins.
Such halogen-containing resins include polyvinyl chloride, polyvinylidene chloride, chlorinated polyolefin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinylidene chloride copolymer resin, etc.
In particular, chlorine-containing resins are most suitable. The amount of the polyester plasticizer used in the present invention is usually about 5 to 100 parts by weight per 100 parts by weight of the halogen-containing resin.
200 parts by weight, preferably 20-100 parts by weight is optimal. Furthermore, the polyester plasticizer of the present invention is a known plasticizer used in the field of processing polyvinyl chloride resins, such as phthalate esters such as DOP; adipic esters such as di2-ethylhexyl adipate; TOTM It can also be used in combination with trimellitic acid esters such as; epoxidized fatty acid esters; chlorinated fatty acid esters; chlorinated paraffins; phosphoric acid esters; and polyesters such as adipic acid. Furthermore, the polyester plasticizer of the present invention can be used in combination with other additives such as stabilizers, fillers, pigments, etc. The invention will now be explained by way of example. Of course, these do not limit the invention. In addition, the number of parts used in the synthesis examples and practices represents parts by weight. Synthesis Example 1 2055 parts of isophthalic acid, 1433 parts of neopentyl glycol, and ε-caprolactone were placed in a 4-necked flask equipped with a dehydration esterification device, a stirring blade, a thermometer, etc.
12,000 parts of tetrabutyl titanate and 0.15 parts of tetrabutyl titanate were charged and reacted under nitrogen atmosphere at 220°C for 70 hours with stirring, and water produced in the reaction system by the esterification reaction was removed. As a result, the reaction rate of ε-caprolactone was 99.8%, the hue (APHA) was 70, and the acid value was 99.8%.
A polyester resin having a hydroxyl value of 1.29 and a hydroxyl value of 13.34 was obtained.
The reactive residues of ε-caprolactone were 85%, and the number average molecular weight was about 8,000. Synthesis Example 2 3650 parts of isophthalic acid was added to the same apparatus as in Example 1.
2463 parts of neopentyl glycol, 9750 parts of ε-caprolactone, and 0.16 parts of tetrabutyl titanate were charged and reacted at 220° C. for 80 hours in a nitrogen atmosphere, and the produced water was removed from the reaction system. As a result, a polyester resin having a hue (APHA) of 80, an acid value of 0.82, and a hydroxyl value of 13.26 was obtained. The number average molecular weight was approximately 8,000. Examples The plasticizer obtained in the synthesis example and the plasticizer for comparison were Plaxel H-4 (caprolactone homopolymer molecular weight 40,000), and 0.5% bisphenol A was added and dissolved as an antioxidant to DOP, and the following plasticizers were used as plasticizers. A sheet was prepared according to the basic formulation and molding conditions. (Basic composition) Polyvinyl chloride (degree of polymerization 1450) 100 parts Plasticizer 60 parts Tribasic lead sulfate 5 parts Lead stearate 1 part (molding conditions) Roll (6″φ): 160°C x 8 minutes Breath (1 mm thickness) ): 170°C x 4 minutes The following physical property tests were conducted on these sheets, and the results are shown in Table 1. (1) Hardness (JIS Spring A Scale): JIS-
I followed K6301. (2) High humidity bleed test A roll sheet with a thickness of 0.3 mm was separately prepared using the above basic composition. 70℃ as a 40mm x 100mm test piece,
The degree of bleed of the test piece was evaluated after 10 days of being left in a constant temperature and humidity chamber at 98% RH. However, ○: No bleeding phenomenon is observed. x: Bleeding phenomenon was observed. (3) Migration test A 1 mm thick disk-shaped test piece with the same diameter was placed on both sides of an ABS, styrene, or polyethylene disk with a thickness of 2 mm and a diameter of 60 mm, and a 500 g load was applied in an atmosphere of 98°C. After leaving it for 7 days,
The surface conditions of ABS, styrene, and polyethylene were observed. However, 〇: No migration phenomenon is observed. ×: A migration phenomenon was observed. 【table】

Claims (1)

[Claims] 1 Compositional formula () [A] _l [B] _n [C] _o ... () (wherein A is an aromatic dicarbonate having a straight chain or side chain having 8 to 16 or 36 carbon atoms) Represents an acid residue; B represents a diol residue having a linear or side chain having 2 to 24 carbon atoms; C represents a 6-hydroxycaproic acid residue; however, each of these residues It is bonded by an ester bond and distributed randomly and/or block-like throughout the molecule, l, m, and n have values larger than 0, and 6-hydroxycaproic acid residues are 20 to 98
(including weight percent) and has a number average molecular weight of approximately 2000 to
200000 polyester plasticizer.